JPH06212106A - Ink for ink jet recording - Google Patents

Abstract

(57) [Summary] [Object] To provide a pigment-based inkjet recording ink which has excellent ink storage stability, does not cause nozzle clogging, and has no printing unevenness. [Structure] Pigment, sugar, its derivative and hydroxyl group
An ink for inkjet recording comprising a resin emulsion and a component selected from polyols having one or more polyols.

Description

Detailed Description of the Invention

[Background of the Invention]

FIELD OF THE INVENTION The present invention relates to an aqueous pigment-dispersed ink composition suitable for an ink jet recording system.

[0002]

2. Description of the Related Art Conventionally, as an ink jet recording ink, a dye-based ink composition basically comprising a dye and an aqueous medium is known. It has been pointed out that these inks are inferior in light resistance and water resistance of printed matters due to the properties of dyes. Therefore, in order to solve this problem, an ink using a pigment instead of a dye has been proposed.

On the other hand, the properties required of ink jet recording inks are that the physical properties do not change during long-term storage, that fine nozzles are not clogged, that the density of the printed matter is high and clear, and that the printed matter is clear. Shelf life (water resistance,
Light resistance, etc.) is required. In particular, pigment-based inks are required to have storage stability (that is, to disperse the pigment stably for a long period of time) and to prevent nozzle clogging during printing or during restarting after printing is interrupted.

The following pigment inks have been proposed.

For example, Japanese Patent Publication No. 62-1426 discloses an ink in which a pigment and a resin emulsion are dispersed in water. It is said that the storage stability of the pigment ink is improved by adding an emulsion made of a water-insoluble synthetic resin. However, the resin, which is a water-insoluble component in the ink, tends to solidify at the tip of the nozzle and cause clogging.

Japanese Unexamined Patent Publication (Kokai) No. 55-157668 discloses that dispersion stability can be maintained even at a relatively low viscosity by dispersing a pigment in a water-insoluble resin emulsion dispersion. In addition, Japanese Patent Laid-Open No. 1-21708
Japanese Patent Laid-Open No. 8 discloses that the storage stability and fluidity of ink are improved by using an emulsion having a specific film forming temperature. However, these inks also had insufficient stability at low and high temperatures, and clogging still occurred.

Similarly, inks using a resin emulsion are disclosed in Japanese Patent Laid-Open Nos. 3-160068 and 4-1998.
Although disclosed in Japanese Patent No. 18462, there is room for further improvement in ink stability even with these inks.

Further, in Japanese Patent Laid-Open No. 2-18427,
It is described to add inositol to the ink in order to improve nozzle clogging. However, due to the hygroscopicity of inositol, the ink of this ink is inferior in water rub resistance (that is, when the printed surface is touched, characters are rubbed or ink is attached to a hand or a finger).

Further, it has been pointed out that in the ink jet recording ink using the pigment, there is a problem called "unevenness of printing" which is not seen in the ink using the dye. Print unevenness is an important problem in applications where not only letters but also figures and graphs must be printed.

The present inventors attempted to improve the print unevenness by increasing the pigment concentration and printing with an excessive ink discharge amount, but the improvement was not sufficiently obtained. Therefore,
It is considered that this printing unevenness largely depends on the ink composition.

[Summary of the Invention]

DISCLOSURE OF THE INVENTION The present invention is a pigment-based ink jet recording ink, which enables printing without printing unevenness, storage stability of ink, and reliability that does not cause nozzle clogging. It is an object of the present invention to provide an ink having Still another object of the present invention is to provide an ink for ink jet recording, which has a high print density and is capable of producing a print having excellent quick-drying properties and water rub resistance. The present inventors have surprisingly found that the above object is achieved by adding a compound having a specific hydroxyl group and a resin emulsion to an ink composition.

[0012]

Therefore, the ink jet recording ink according to the present invention comprises the following components. (A) Pigment (b) Component selected from sugar, its derivative and polyol having 5 or more hydroxyl groups (c) Resin emulsion

[Detailed Description of the Invention] Component a) As the pigment added to the ink according to the present invention, an inorganic pigment or an organic pigment can be used without particular limitation.
As the inorganic pigment, in addition to titanium oxide and iron oxide, carbon black produced by a known method such as a contact method, a furnest method or a thermal method can be used. The organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigment, thioindigo pigment, isoindolinone pigment, quinophthalone pigment, etc.), dye chelate (for example, basic dye type chelate,
Acid dye type chelates, etc.), nitro pigments, nitroso pigments, aniline black, etc. can be used.

According to a preferred embodiment of the present invention, among these pigments, those having a good affinity for water are preferably used.

The particle size of the pigment is preferably 10 μm or less, more preferably 0.1 μm or less.

Further, according to a preferred embodiment of the present invention, this pigment is preferably added to the ink composition as a pigment dispersion liquid obtained by dispersing the pigment in a solvent with a dispersant. As a preferable dispersant, a known dispersant used for preparing a conventionally known pigment dispersion liquid, for example, a polymer dispersant or a surfactant can be used.

Preferred examples of the polymer dispersant include natural polymers, and specific examples thereof include proteins such as glue, gelatin, casein and albumin; natural gums such as gum arabic and tragacanth; savonin and the like. Glucosides; alginic acid and alginic acid derivatives such as propylene glycol alginate, triethanolamine alginate and ammonium alginate; methyl cellulose, carboxymethyl cellulose,
Examples thereof include cellulose derivatives such as hydroxyethyl cellulose and ethyl hydroxyethyl cellulose.

Further, synthetic polymers can be mentioned as preferable examples of the polymer dispersant. Polyvinyl alcohols; polyvinyl pyrrolidones; polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate. -Acrylic resin such as acrylic acid ester copolymer and acrylic acid-acrylic acid alkyl ester copolymer; styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer Styrene-acrylic acid resins such as polymers, styrene-α-methylstyrene-acrylic acid copolymers, styrene-α-methylstyrene-acrylic acid-acrylic acid alkyl ester copolymers; styrene-maleic acid; styrene-maleic anhydride Acid; vinyl naphthale -Acrylic acid copolymer; Vinyl naphthalene-maleic acid copolymer; Vinyl acetate-ethylene copolymer, Vinyl acetate-fatty acid vinyl ethylene copolymer, Vinyl acetate maleate ester copolymer, Vinyl acetate crotonic acid copolymer Examples thereof include coalesce, vinyl acetate-based copolymers such as vinyl acetate acrylic acid copolymer, and salts thereof. Among these, a copolymer of a monomer having a hydrophobic group and a monomer having a hydrophilic group, and a polymer composed of a monomer having both a hydrophobic group and a hydrophilic group are particularly preferable. Examples of the above salts include salts with diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol, morpholine and the like. The weight average molecular weight of these copolymers is preferably 3,000 to 30,000, more preferably 5,000 to 15,000.

Examples of surfactants preferable as the dispersant are fatty acid salts, higher alkyl dicarboxylic acid salts, higher alcohol sulfuric acid ester salts, higher alkyl sulfonates, condensates of higher fatty acids and amino acids, sulfosuccinic acid esters. Anionic surfactants such as salts, naphthenates, liquid fatty oil sulfuric acid ester salts and alkylallyl sulfonates; cationic surfactants such as fatty acid amine salts, quaternary ammonium salts, sulfonium salts and phosphoniums; polyoxyethylene Examples include nonionic surfactants such as alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and polyoxyethylene sorbitan alkyl esters.

The amount of these dispersants added is preferably in the range of 0.06 to 3% by weight, more preferably 0.125 to 3% by weight, based on the pigment 1.

Component b) Examples of saccharides added to the ink according to the present invention include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose,
Mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbit), maltose, cellobiose, lactose, sucrose, trehalose, maltotriose and the like can be mentioned. Here, the term "polysaccharide" means a sugar in a broad sense, and is meant to include substances widely existing in nature such as alginic acid, α-cyclodextrin, and cellulose.

The derivatives of these sugars include reducing sugars of the above-mentioned sugars (for example, sugar alcohol (general formula H
OCH ₂ (CHOH) nCH ₂ OH (where n = 2 to
(Representing an integer of 5)), deoxy sugar, etc.), oxidation (eg, aldonic acid, uronic acid, etc.), dehydrated sugar derivative (eg, glycoceene, etc.), amino sugar, thio sugar and the like. Sugar alcohol is particularly preferable, and specific examples thereof include maltitol, sorbitol and the like.

The polyol having 5 or more hydroxyl groups added to the ink according to the present invention means a hydrocarbon having 5 or more, preferably 5 to 12 hydroxyl groups in the cyclic carbon chain. . A preferred example of such a hydrocarbon is inositol.

Component c) The resin emulsion added to the ink according to the present invention means an emulsion in which the continuous phase is water and the dispersed phase is the following resin component. Examples of the resin component of the dispersed phase include acrylic resin, vinyl acetate resin, styrene-butadiene resin, vinyl chloride resin, acrylic-styrene resin, butadiene resin, and styrene resin.

According to a preferred embodiment of the present invention, this resin is preferably a polymer having both a hydrophilic portion and a hydrophobic portion. The particle size of these resin components is not particularly limited as long as it forms an emulsion,
nm or less is preferable, and more preferably 5 to 100 n
It is about m.

These resin emulsions can be obtained by mixing resin particles with water, optionally together with a surfactant. For example, an acrylic resin or a styrene-acrylic resin emulsion is (meth)
It can be obtained by mixing acrylic acid ester or styrene, (meth) acrylic acid ester, optionally (meth) acrylic acid, and a surfactant with water. The mixing ratio of the resin component and the surfactant is usually 1
It is preferably about 0: 1 to 5: 1. When the amount of the surfactant used is less than the above range, it is difficult to obtain an emulsion, and when the amount exceeds the above range, the water resistance of the ink tends to decrease and the penetrability tends to deteriorate, such being undesirable. The surfactant is not particularly limited, but preferable examples thereof include anionic surfactants (eg, sodium dodecylbenzansulfonate, sodium lalaurylate, ammonium salt of polyoxyethylene alkyl ether sulfate, etc.), nonionic surfactants. (For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamide, etc.), and these may be used alone or Two or more kinds can be mixed and used.

The ratio of the resin as the disperse phase component to water is 60 to 400 parts by weight, preferably 100 to 200 parts by weight, relative to 100 parts by weight of the resin.

As such a resin emulsion, a known resin emulsion can be used. For example, JP-B-62-1426, JP-A-3-56573, JP-A-3-79678, and JP-A-3-160068. The resin emulsions described in JP-A-4-18462 can be used as they are.

It is also possible to use a commercially available resin emulsion, for example, Microgel E-100.
2, E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint Co., Ltd.), Boncoat 4001
(Acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.), Boncoat 5454 (styrene-acrylic resin emulsion, manufactured by Dainippon Ink and Chemicals, Inc.), SAE1014 (styrene-acrylic resin emulsion, manufactured by Nippon Zeon Co., Ltd.) ), Cybinol SK
-200 (acrylic resin emulsion, manufactured by Saiden Chemical Co., Ltd.), and the like.

According to a preferred embodiment of the present invention, the resin emulsion preferably has a minimum film forming temperature (MFT) of 50 ° C. or higher.

Ink Composition The ink according to the present invention comprises 0.1% of the above-mentioned component (b).
-40% by weight, and more preferably 0.5-30% by weight. If the addition amount is less than the above range, the effect of the addition cannot be obtained, and if it exceeds the above range, it may be difficult to dissolve the component (b) in water, which is not preferable.

In the ink according to the present invention, the resin emulsion described above is used as the resin component.
The content is preferably 1 to 40% by weight, more preferably 1 to 25% by weight. If the addition amount is less than the above range, the effect of the addition cannot be obtained, and if it exceeds the above range, the print density may be lowered and the viscosity of the ink may be too high, which is not preferable.

The amount of pigment added to the ink is 0.5 to
The amount is preferably about 25% by weight, more preferably about 2 to 15% by weight.

In the ink according to the present invention, the ink composition forms a very thin and brittle film at the tip of the nozzle. This coating prevents further evaporation of components such as water from the ink composition and prevents clogging of the nozzle due to precipitation of solid components. On the other hand, since this coating is thin and brittle, it can be easily torn by a cleaning operation (return operation) that is usually performed, and the next printing can be immediately performed. Further, according to the ink of the present invention, it is possible to obtain a print having a high print density and good water rub resistance. Not being bound by theory, the resin emulsion and component (b) are adsorbed on the pigment particles, increasing the apparent particle size, and as a result, it becomes difficult for the pigment to penetrate between the fibers of the paper and the ink permeability is increased. It is considered that the reason is that it is relaxed and the pigment particles can be well retained on the paper fiber. More interestingly, the ink according to the present invention has excellent storage stability. It is considered that the adsorption of the resin emulsion and the component (b) on the pigment particles stabilizes the dispersion of the pigment and improves the storage stability of the ink.

Furthermore, according to a preferred embodiment of the present invention, the ink according to the present invention preferably has a weight ratio of resin emulsion: component (b) in the range of 1: 0.5 to less than 1:50, and Preferably from 1: 0.5 to 1:40
Is the range. By combining this weight ratio with a resin emulsion having a minimum film forming temperature of 50 ° C. or higher, the advantages of the ink according to the present invention described above can be further enjoyed.

Furthermore, according to a preferred embodiment of the present invention, the ink according to the present invention comprises the raw material, the component (a) and the resin emulsion, and the weight ratio of the resin component in the pigment: resin emulsion is preferably 1: 0.1. To 1: 2, more preferably 1: 0.1 to 1: 1.5, and the weight ratio of component (b): pigment and resin component in the emulsion is preferably 1: 0.1. To 1: 2, more preferably 1: 0.18 to 1: 2.

Also, according to a preferred embodiment of the present invention, the ink according to the present invention preferably further comprises a wetting agent. Preferred examples of the wetting agent include diethylene glycol, polyethylene glycol, polypropylene glycol, ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,
6-hexanetriol, thioglycol, hexylene glycol, glycerin, trimethylolethane, trimethylolpropane, urea, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. In particular, those having an ethylene oxide group are preferable, and diethylene glycol is most preferable. Further, in addition to these wetting agents, it is preferable to further add a low boiling point organic solvent. Preferred examples of the low boiling point organic solvent include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, iso-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol. Examples thereof include monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether and triethylene glycol monoethyl ether. A monohydric alcohol is particularly preferable.

The amount of these wetting agents added is 0.5 in the ink.
A range of -40% by weight, preferably 2-20% by weight is suitable. Further, the addition amount of the low boiling point organic solvent is appropriately in the range of 0.5 to 10% by weight of the ink, preferably 1.5 to 6% by weight.

According to a further preferred embodiment according to the invention, the total amount of pigment and resin component in the resin emulsion:
It is preferable that the weight ratio of the dispersant is 1: 0.02 to 1: 0.5 and the weight ratio of the dispersant: component (b) is 1: 0.5 to 50.

Since it is considered that the resin emulsion described above also functions as a dispersant, the addition of a further resin emulsion may replace the addition of the dispersant.

Furthermore, in order to improve various physical properties of the ink, suitable additives can be added to the ink according to the present invention, if necessary. Specific examples of the additive include a viscosity adjusting agent, a surface tension adjusting agent, a pH adjusting agent, an antifungal agent and an antiseptic agent.

The ink according to the present invention can be produced by dispersing and mixing the above components by a suitable method. Preferably, the mixture obtained by removing the organic solvent and volatile components is treated with a suitable disperser (for example, ball mill, sand mill, attritor, roll mill, agitator mill,
(Henschel mixer, colloid mill, ultrasonic homogenizer, jet mill, ong mill, etc.) to obtain a homogeneous composition, and then the organic solvent and the volatile component are preferably added. Thereafter, filtration (preferably vacuum or pressure filtration using a metal filter, a membrane filter or the like) or centrifugation is performed in order to remove coarse particles and foreign matter that cause clogging.

[0043]

The present invention will be explained in more detail by the following examples, but the present invention is not limited to these. In the examples, MFT represents the minimum film forming temperature.

Example 1 Carbon black MA7 2% by weight (manufactured by Mitsubishi Kasei Co., Ltd.) Styrene-maleic anhydride copolymer 4% by weight (dispersant) Microgel E-1002 25% by weight (styrene-acrylic resin emulsion) , Resin component 1
9.9%, MFT = about 80 ° C., manufactured by Nippon Paint Co., Ltd.) α-Cyclodextrin 14% by weight Diethylene glycol 5% by weight Ethanol 5% by weight Pure water 45% by weight The above components except diethylene glycol and ethanol are mixed, and a sand mill ( In Yasukawa Seisakusho, glass beads (diameter 1.7 mm, 1.5 times amount (weight) of the mixture) were dispersed together for 2 hours. Then remove the glass beads,
Add diethylene glycol and ethanol at room temperature for 20
Stir for minutes. An ink for inkjet recording was obtained by filtering with a 5 μm membrane filter.

Example 2 Carbon black MA100 3% by weight (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) Porovinyl alcohol 0.5% by weight (dispersant) Boncoat 4001 2% by weight (acrylic resin emulsion, resin component 50%, MF)
T = 5 ° C., manufactured by Dainippon Ink and Chemicals, Inc.) Sucrose 15% by weight Glycerin 10% by weight n-Propanol 2% by weight Pure water 67.5% by weight Glycerin, the above components except n-propanol are mixed, and a sand mill ( In Yasukawa Seisakusho), it was dispersed for 2 hours together with zirconium beads (diameter: 1.2 mm, 0.8 times amount (weight) of the mixture). Thereafter, the beads were removed, glycerin and n-propanol were added, and the mixture was stirred at room temperature for 20 minutes. An ink for inkjet recording was obtained by filtering with a 5 μm membrane filter.

Example 3 Carbon black # 40 2.5% by weight (manufactured by Mitsubishi Kasei Co., Ltd.) Styrene-acrylic acid copolymer 2% by weight (dispersing agent) Microgel E-5002 0.85% by weight (styrene- Acrylic resin emulsion, resin component 2
9.2%, MFT = about 80 ° C., manufactured by Nippon Paint Co., Ltd.) Inositol 10% by weight 2-pyrrolidone 4% by weight Ethanol 5% by weight Pure water 75.65% by weight 2-pyrrolidone, the above components except ethanol are mixed. ,
In a sand mill (Yasukawa Seisakusho), glass beads (diameter 1.0 mm, 1.2 times amount (weight) of the mixture) were dispersed for 2 hours. After that, the glass beads were removed, 2-pyrrolidone and ethanol were added, and the mixture was stirred at room temperature for 20 minutes.
An ink for inkjet recording was obtained by filtering with a 5 μm membrane filter.

Example 4 C. I. Pigment Black 15% by weight Polyvinylpyrrolidone 1% by weight (dispersant) Boncoat 5454 15% by weight (styrene-acrylic resin emulsion, resin component 4
5%, MFT = 4 ° C., manufactured by Dainippon Ink and Chemicals, Inc.) Xylose 6% by weight Glycerin 10% by weight n-Propanol 4% by weight Pure water 59% by weight The above components except glycerin and n-propanol are mixed, and a sand mill is used. 2 with glass beads (diameter 1.7 mm, 1.5 times amount (weight) of mixture) in (Yasukawa Seisakusho)
Dispersed for hours. After that, the glass beads were removed, diethylene glycol and ethanol were added, and the mixture was stirred at room temperature for 20 minutes. An ink for inkjet recording was obtained by filtering with a 5 μm membrane filter.

Example 5 Carbon black MA7 2% by weight Styrene-acrylic acid copolymer (dispersant) 0.8% by weight Microgel E-1002 3% by weight Sucrose 5.6% by weight Diethylene glycol 5% by weight Ethanol 5% by weight Pure water 78.6% by weight The above components except diethylene glycol and ethanol are mixed and dispersed in a sand mill (Yasukawa Seisakusho) with glass beads (diameter 1.7 mm, 1.5 times the weight of the mixture (weight)) for 2 hours. It was Then remove the glass beads,
Add diethylene glycol and ethanol at room temperature for 20
Stir for minutes. An ink for inkjet recording was obtained by filtering with a 5 μm membrane filter.

Example 6 Carbon black MA100 3% by weight Polyvinyl alcohol (dispersant) 0.5% by weight SAE1014 5% by weight (styrene-acrylic resin emulsion, resin component 4
0%, MFT = 70 to 90 ° C., manufactured by Nippon Zeon Co., Ltd.) Sorbit 5% by weight Glycerin 10% by weight n-Propanol 2% by weight Pure water 69.5% by weight The above components except glycerin and n-propanol are mixed, 2 in a sand mill (Yasukawa Seisakusho) with glass beads (diameter 1.2 mm, 0.8 times the weight of the mixture (weight))
Dispersed for hours. After that, the glass beads were removed, glycerin and n-propanol were added, and the mixture was stirred at room temperature for 20 minutes. An ink for inkjet recording was obtained by filtering with a 5 μm membrane filter.

Example 7 Carbon Black Raven 1080 2.4 wt% (Colombian Carbon Co., Ltd.) Styrene-maleic anhydride copolymer (dispersant) 0.5 wt% Cybinol SK-200 0.88 wt% ( Acrylic resin emulsion, resin component 49.5%,
MFT> 80 ° C, manufactured by Saiden Chemical Co., Ltd.) Maltotriose 15% by weight Urea 4% by weight Ethanol 5% by weight Pure water 72.22% by weight The above components except urea and ethanol are mixed in a sand mill (Yasukawa Seisakusho). , Glass beads (diameter 1.0 mm, 1.2 times amount (weight) of the mixture) were dispersed for 2 hours. After that, the glass beads were removed, urea and ethanol were added, and the mixture was stirred at room temperature for 20 minutes. An ink for inkjet recording was obtained by filtering with a 5 μm membrane filter.

Example 8 C. I. Pigment Black 18% by weight Polyvinylpyrrolidone 1% by weight (Dispersant) Boncoat 5454 5% by weight Maltitol 10% by weight 1,5-pentanediol 10% by weight n-Propanol 4% by weight Pure water 62% by weight 1,5-pentane The above components other than the diol and n-propanol were mixed and dispersed in a sand mill (Yasukawa Seisakusho) together with glass beads (diameter 1.7 mm, 1.5 times amount (weight) of the mixture) for 2 hours. Thereafter, the glass beads were removed, 1,5-pentanediol and n-propanol were added, and the mixture was stirred at room temperature for 20 minutes. An ink for inkjet recording was obtained by filtering with a 5 μm membrane filter.

Example 9 Carbon black MA100 5% by weight Potassium acrylate / acrylonitrile copolymer (dispersing agent) 1% by weight Microgel E-1002 4% by weight Sucrose 8% by weight Glycerin 8% by weight Ethanol 6% by weight Pure water 68 Wt% The ingredients were mixed in a jet mill. It was confirmed by microscopic observation that the particle size was 1 μm or less. Mix 3
An inkjet recording ink was obtained by pressure filtration with a μm membrane filter.

Thereafter, in the same manner as in Example 9, Example 10
Ink jet recording inks Nos. 13 to 13 were obtained.

Example 10 Carbon black MA100 4% by weight Styrene-acrylic acid copolymer (dispersant) 1.2% by weight Microgel E-1002 8% by weight α-cyclodextrin 3% by weight Diethylene glycol 12% by weight 2-propanol 3% by weight Pure water 68.8% by weight

Example 11 Carbon black MA7 2% by weight Styrene-maleic acid copolymer 0.5% by weight (dispersing agent) SG-60 1.2% by weight (styrene-acrylic resin emulsion, resin component 4)
1%, MFT = 92 ° C., manufactured by Gifu Ceramic Manufacturing Co., Ltd.) Sucrose 10% by weight Urea 2% by weight 2-Propanol 5% by weight Pure water 79.3% by weight

Example 12 Carbon black MA7 2% by weight Styrene-maleic acid copolymer 5% by weight (dispersant) Polyvinylpyrrolidone 1% by weight (dispersant, average molecular weight about 40,000 manufactured by Tokyo Chemical Industry Co., Ltd.) SEE- 975% by weight (styrene-acrylic acid ester-based resin emulsion,
Resin component 40%, MFT = 50-80 ° C., manufactured by Nippon Paint Co., Ltd.) Xylose 1.5% by weight Polyethylene glycol 8% by weight Ethanol 4% by weight Pure water 71% by weight

Example 13 Pigment KET Red 309 3% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Potassium acrylate / acrylonitrile (dispersing agent) 0.5% by weight Denkapovar 1% by weight (dispersing agent, Electrochemical Industry Co., Ltd. AS-467A 4.3% by weight (styrene-acrylic resin emulsion, resin component 4)
6%, MFT = 70 to 90 ° C., manufactured by Daicel Chemical Industries, Ltd.) Inositol 10% by weight Diethylene glycol 5% by weight 1-Propanol 5% by weight Pure water 71.2% by weight

Example 14 Carbon black MA100 2% by weight Acrylic acid / acrylonitrile copolymer salt (dispersant) 0.2% by weight Microgel E-1002 2.5% by weight Maltose 1.2% by weight Diethylene glycol 5% by weight Ethanol 3% by weight Pure water 86.1% by weight The components were mixed by a jet mill. It was confirmed by microscopic observation that the particle size was 1 μm or less. Mix 3
An inkjet recording ink was obtained by pressure filtration with a μm membrane filter.

Hereinafter, in the same manner as in Example 14, Example 1
5 to 21 ink jet recording inks were obtained.

Example 15 Carbon black MCF-88 5% by weight (manufactured by Mitsubishi Kasei Co., Ltd.) Salt of acrylic acid / acrylonitrile copolymer (dispersing agent) 2.2% by weight SEE-9 0.75% by weight inositol 3 % By weight Ethylene glycol 5% by weight 1-Propanol 1% by weight Urea 1% by weight Pure water 82.05% by weight

Example 16 Carbon black MA7 4% by weight Polyvinylpyrrolidone 0.8% by weight (dispersant, average molecular weight about 40,000, manufactured by Tokyo Chemical Industry Co., Ltd.) Microgel E-1002 15.1% by weight Sucrose 4 % By weight Urea 2.2% by weight 2-propanol 2% by weight Pure water 71.9% by weight

Example 17 Carbon black Raven 150 3% by weight (Colombian Carbon Co., Ltd.) Styrene-acrylic acid copolymer salt (dispersant) 0.18% by weight SG-60 7.3% by weight Solbit 2% by weight % Urea 3% by weight Glycerin 5% by weight 1-Butanol 0.5% by weight Pure water 79.02% by weight

Example 18 Pigment KETBLUEEX-1 5% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Styrene-acrylic acid copolymer salt 1% by weight (dispersant) Macrogel E-1002 1.5% by weight galactose 2% by weight Sucrose 7.5% by weight Diethylene glycol 5% by weight Ethanol 4% by weight Pure water 74% by weight

Example 19 Pigment KETYELLOW403 3% by weight (manufactured by Dainippon Ink and Chemicals, Inc.) Salt of styrene-acrylic acid copolymer (dispersant) 0.4% by weight SAE1014 5% by weight Maltitol 0.5% by weight Alginic acid 0.5% by weight Urea 2% by weight Diethylene glycol 5% by weight Ethanol 2% by weight Pure water 81.6% by weight

Example 20 Carbon black MA7 4% by weight Styrene-acrylic acid copolymer salt (dispersant) 0.8% by weight Cybinol SK-200 1.2% by weight Glucose 12% by weight Thiourea 2% by weight Ethanol 3 Weight% Pure water 77% by weight

Example 21 Carbon black MA7 4% by weight Styrene-acrylic acid copolymer salt (dispersing agent) 0.8% by weight Microgel E1002 3% by weight SAE1014 1.3% by weight Maltitol 4.2% by weight Urea 3% by weight Diethylene glycol 5% by weight Ethanol 1.5% by weight Pure water 77.2% by weight

Comparative Example 1 Carbon black MA100 10% by weight Gelatin (dispersing agent) 4% by weight Inositol 7% by weight Ethylene glycol 15% by weight Ethanolamine 1% by weight Pure water 60% by weight Sand mill (Yasukawa Seisakusho) In, it was dispersed for 2 hours together with glass beads (diameter 1.0 mm, 1.2 times amount (weight) of the mixture). Then, the mixture was filtered with a 5 μm membrane filter to obtain an inkjet recording ink.

Comparative Example 2 C.I. I. Pigment Black 18 wt% Lunox 1500A 3.4 wt% (Toho Chemical Co., Ltd., anionic surfactant) Nonal 310 1 wt% (Toho Chemical Co., anionic surfactant) Primal AC-61 18 wt% ( Acrylic resin emulsion, resin component 46%, MF
T = 17 ° C., manufactured by Nippon Acrylic Co., Ltd.) Ethylene glycol 7% by weight Pure water 62.6% by weight The components were mixed by a jet mill. It was confirmed by microscopic observation that the particle size was 1 μm or less. Mix 3
An inkjet recording ink was obtained by pressure filtration with a μm membrane filter.

Comparative Example 3 Carbon black MA7 3% by weight Styrene-maleic anhydride copolymer salt (dispersant) 0.1% by weight Microgel E1002 15% by weight Polyethylene glycol 4.5% by weight Urea 7% by weight 1- Propanol 3% by weight Pure water 67.4% by weight In the same manner as in Comparative Example 2, an inkjet recording ink was obtained.

Evaluation Test The properties of the ink jet recording ink obtained above were evaluated as follows. (A) Clogging Inkjet printer HG-5130 (manufactured by Seiko Epson Corporation) was filled with ink, and after continuous printing for 10 minutes, printing was stopped. Printers without caps on the head were used in Examples 1 to 8 and Comparative Examples 1 and 2.
The ink of No. 2 was allowed to stand in an environment of 40 ° C. and 25% RH for 2 weeks, and the inks of Examples 9 to 21 and Comparative Example 3 were allowed to stand at room temperature for one day. After standing, the nozzle was cleaned, and then printing was performed. The clogging characteristic of the ink was evaluated by the number of cleaning operations until the printing equivalent to the initial printing was possible without causing defective printing such as scraping and omission. The results are shown in the table. In the table, when 0 to 5 times of cleaning operation can obtain the same printing as the initial printing- ○ 6 to 10 times of cleaning operation can obtain the same printing as the initial printing- △ Even after 11 or more cleaning operations Cannot be printed equivalent to-

(B) Storage stability 50 cc of ink was placed in a Labran screw tube bottle, the inks of Examples 1 to 8 and Comparative Examples 1 and 2 were at 50 ° C., and the inks of Examples 9 to 2 and Comparative Example 3 were stored. The ink was left at −20 ° C. and 50 ° C. for 2 months and examined for the presence of sediment. The results are shown in the table. In the table, for Examples 1 to 8 and Comparative Examples 1 and 2, no sediment- ○ No sediment-X For Examples 9 to 21 and Comparative Example-3 No sediment at both -20 ° C and 50 ° C- ○ -20 ° C In the case of only, there is sediment- △ At any temperature there is sediment- ×

(C) Water resistance Xerox with an inkjet printer HG-5130
Printing was performed on P paper (registered trademark, manufactured by Xerox Co., Ltd.), and the printed matter was naturally dried for 24 hours. The printed matter is 100c
Immerse in the water of c and change the concentration before and after the macbet
h Measured with PCMII (manufactured by Macbeth). The results are shown in the table. In the table, when the change in OD value before and after immersion is 0.5 or less- ○ When the change in OD value before and after immersion is 0.5 to 1.0- △ Change in OD value before and after immersion is 1.0 or more In case of − ×

(D) Finger touch Xerox with an inkjet printer HG-5130
Printing was performed on P paper (registered trademark, manufactured by Xerox Co., Ltd.), and the printed matter was naturally dried for 24 hours. The printed matter at 25 ° C
It was rubbed with a finger in an environment of 50% RH, and the presence or absence of stains on the print was visually observed. The results are shown in the table. In the table, when stains on the print are not observed- ○ Slight stains on the print occur, but when the characters can be discriminated-△ When the characters cannot be discriminated due to the stain on the print-×

(E) Light fastness Ink jet printer HG-5130 with Xerox
Print on P paper (registered trademark, manufactured by Xerox Co., Ltd.)
The printed matter was naturally dried for 4 hours. The printed matter was irradiated with light using a Xenon Fade Tester XF-15N (manufactured by Shimadzu Corporation) in an environment of 70% RH for 50 hours. Change of color difference of L * a * b before and after light irradiation is CR-12.
It was measured with a one-color color difference meter (manufactured by Minolta Co., Ltd.).

The results are shown in the table. In the table, when ΔE ≦ 10 − ○ When ΔE> 10 − ×

(F) Print Quality (Bleed) With the inkjet printer HG-5130, Xerox
P paper (registered trademark, manufactured by Xerox Co., Ltd.), Rico
py 6000 paper (registered trademark, manufactured by Ricoh Co., Ltd.), X
Erox 4024 paper (registered trademark, manufactured by Xerox Co., Ltd.) and Neenah Bond paper (registered trademark, manufactured by Kimberly Clark Co., Ltd.) were printed, and the occurrence of print bleeding was checked. The results are shown in the table. In the table, clear printing with no bleeding- ○ Whisker-like bleeding- △ Bleeding to the extent that the outline of the character is not clear-x

(G) Print Quality (OD Value) The reflected OD value of the print obtained in the above-mentioned print quality (bleeding) section was measured by Macbeth PCMII. The results are shown in the table.

(H) Quick-drying 100% duty is applied to four types of paper similar to the above-mentioned print quality (bleeding) with an inkjet printer HG-5130.
Printing (solid printing) was performed, and quick dryness was evaluated by the time until the hand was not soiled even if the printing was touched by hand. The result is
As shown in the table. In the table, within 30 seconds- ○ Over 30 seconds- ×

(I) Printing unevenness With the ink jet printer HG-5130, Ricop
y 6000 paper (registered trademark, manufactured by Ricoh Co., Ltd.), Ca
Printing was performed on non-dry paper (registered trademark, manufactured by Canon Inc.) with 100% duty. Macbeth P
Using CMII, OD values at arbitrary 5 points on the printed portion were measured, and the average value was obtained. Repeat this procedure 5 times, 5
The difference between the maximum and minimum of the two averages was calculated. If this difference is less than 0.5, there is no practical problem, and it is preferably less than 0.4. The results are shown in the table.
In the table, the difference in OD value is less than 0.4- ◎ The difference in OD value is 0.4 or more and 0.5 or less- ○ The difference in OD value exceeds 0.5- ×

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

[Table 3]

[0083]

[Table 4]

[0084]

[Table 5]

[0085]

[Table 6] * 1: Does not include resin emulsion * 2: Does not include component (b)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese patent application No. 4-315344 (32) Priority date Hei 4 (1992) November 25 (33) Priority claim country Japan (JP) (72) Inventor Hiroko Hayashi 3-5-3 Yamato, Suwa-shi, Nagano Seiko Epson Corporation (72) Inventor Kiyohiko Takemoto 3-5-5 Yamato, Suwa-shi, Nagano Seiko Epson Corporation (72) Inventor Arada 138-1 Kokubunji, Kokunoji, Gokokuno-cho, Himeji, Hyogo Prefecture (72) Inventor, Kazushi Kawabata 138-1, Kokubunji, Kokubunji, Kokunocho, Himeji-shi, Hyogo

Claims (15)

[Claims] 1. An aqueous inkjet recording ink comprising the following components. (A) Pigment (b) Component selected from sugar, its derivative and polyol having 5 or more hydroxyl groups (c) Resin emulsion 2. The ink jet recording ink according to claim 1, wherein the saccharide as the component (b) is selected from monosaccharides, disaccharides, oligosaccharides and polysaccharides. 3. The sugar derivative as the component (b) is a reducing sugar,
Oxidized sugar, dehydrated sugar derivative, amino sugar or thio sugar,
The ink for inkjet recording according to claim 1. 4. The ink for inkjet recording according to claim 1, wherein the polyol as the component (b) is inositol. 5. The minimum film forming temperature of the resin emulsion is 50 ° C.
The inkjet recording ink according to claim 1, which is the above. 6. The resin emulsion is selected from acrylic resin emulsion, vinyl acetate resin emulsion, vinyl chloride resin emulsion, acrylic-styrene resin emulsion, butadiene resin emulsion and styrene resin emulsion, The ink for inkjet recording according to claim 1. 7. The ink for ink jet recording according to claim 1, wherein the weight ratio of the resin component to the component (b) in the resin emulsion is 1: 0.5 to less than 1:50. 8. The weight ratio of pigment: resin component in the resin emulsion is 1: 0.1 to 1: 2, and component (b):
The ink for inkjet recording according to claim 1, wherein the weight ratio of the total amount of the pigment and the resin component in the emulsion is 1: 0.1 to 1: 2. 9. The resin component of the resin emulsion is 0.1 to 4
The inkjet recording ink according to claim 1, wherein the ink comprises 0% by weight. 10. The ink for ink jet recording according to claim 1, which comprises 0.1 to 40% by weight of the component (b). 11. The ink jet recording ink according to claim 1, further comprising a wetting agent. 12. The ink for ink jet recording according to claim 11, further comprising a low boiling point organic solvent. 13. The ink jet recording ink according to claim 1, wherein the pigment is a pigment dispersion obtained by dispersing the pigment in a solvent with a dispersant. 14. A weight ratio of a total amount of a pigment and a resin component in a resin emulsion to a dispersant is 1: 0.02 to 1: 0.5.
And the weight ratio of dispersant: component (b) is 1: 0.
The ink for inkjet recording according to claim 13, which is 5 to 50. 15. The ink jet recording ink according to claim 13, wherein the pigment dispersion further comprises an amine.